KR102623827B1 - Optical filter and imaging apparatus - Google Patents

Abstract

(assignment)
An infrared cut filter provided with a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass.
(Solution)
An absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; A bonding layer having a single-layer structure; and a resin film, wherein the resin film is provided on the absorption glass substrate through a bonding layer, and the bonding layer includes Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms. Or, an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; and a resin film, wherein the resin film contains Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms, and the resin film is provided on an absorption glass substrate.

Description

Optical filter and imaging device {OPTICAL FILTER AND IMAGING APPARATUS}

The present invention relates to optical filters and imaging devices.

In imaging devices using solid-state imaging elements such as CCD or CMOS image sensors mounted on digital still cameras (DSC: Digital Still Cameras) such as compact digital cameras and digital SLR cameras, visible light is used to reproduce color tones well and obtain clear images. A so-called infra-red cut filter (IRCF (Infra-Red Cut Filter)) that transmits and blocks ultraviolet light and near-infrared light is used (for example, see Patent Document 1 (Japanese Patent Laid-Open No. 2014-148567)).

Figure 1 is a schematic diagram of a camera module constituting a DSC, where Figure 1(a) is a schematic diagram of a camera module according to a compact digital camera mounted on a smartphone, etc., and Figure 1(b) is a schematic diagram of a camera module according to a digital SLR camera. This is a schematic explanation of the module.

In the camera module shown in FIG. 1(a), ultraviolet light and near-infrared light are selectively reflected by an infrared cut filter (IRCF) 1 among the light transmitted through the lens L, and a visible light range tailored to the human visual sensitivity characteristics is provided. Only light is selectively introduced into the module and accepted into the image sensor (IC). Likewise, in the camera module shown in FIG. 1(b), ultraviolet light and near-infrared light are selectively reflected by the infrared cut filter (IRCF) 1 among the light transmitted through the lens L, and then the cover glass (CG) By removing α-rays, the intrusion of dust is suppressed, and only light in the visible light range tailored to human visibility characteristics is selectively introduced into the module and accepted into the image sensor (IC).

As the infrared cut filter (IRCF), a reflective film (UVIR film) is provided on the upper surface side (light incident surface side) of the glass substrate, and an anti-reflective film (AR film) is provided on the lower surface side (light exit surface side) of the glass substrate. It was mainstream.

FIG. 2(a) is a schematic diagram showing the structure of a conventional infrared cut filter (IRCF) 1. In the infrared cut filter (IRCF) 1 shown in FIG. 2(a), the glass substrate 3 A reflective film (UVIR film) 2 is provided on the upper surface side (light incident surface side), and an anti-reflective film (AR film) 4 is provided on the lower surface side (light exit surface side) of the glass substrate 3, so that incident light occurs from the top. Among the types of light, ultraviolet light and near-infrared light are selectively reflected by the reflective film (2), and only light in the visible light range tailored to human visibility characteristics is transmitted through the glass substrate (3) and the anti-reflective film (AR film) (4). , it is emitted from the bottom of the anti-reflection film (AR film) 4.

However, in response to the demand for thinner digital still cameras, various component parts are becoming smaller and shorter, and the image sensor is also optically designed to allow more oblique light to enter the camera. On the other hand, since the reflection-type infrared cut filter (IRCF) has a high dependence on the wavelength of light, when the incident angle of light increases, a phase shift occurs in which the cut-off frequency is shifted toward the short wavelength side, so that the light passing near the center of the lens and the peripheral portion In the light that has passed through the infrared cut filter (IRCF), the angle of incidence of the light incident on the light is different, so it is easy to cause a decrease in color reproducibility due to interference misalignment.

For this reason, the burden on the reflective film (UVIR film) is reduced by separately providing an absorbing resin film in addition to the reflecting film (UVIR film) as the infrared cut filter (IRCF), or by using a light-absorbing glass substrate (absorbing glass substrate) together. In addition, a hybrid type infrared cut filter (IRCF) that can exhibit excellent oblique incidence characteristics while more effectively reducing ultraviolet light and near-infrared light in incident light is being studied.

Figure 2(b) is a schematic diagram showing a structural example of the hybrid type infrared cut filter (IRCF) 1. In the infrared cut filter (IRCF) 1 shown in Figure 2(b), ultraviolet light and A reflective film (UVIR film) 2 is provided on the upper surface side (light incident surface side) of the absorption glass substrate 3' that absorbs at least one side of the near-infrared light, and the lower surface side of the absorption glass substrate 3' ( On the light exit surface side), an absorption resin film 5 and an anti-reflection film (AR film) 4 that absorb ultraviolet light or near-infrared light are sequentially provided, and the reflection film (UVIR film) 2 and the absorption glass substrate ( By using 3') and the absorption resin film 5 together, the ultraviolet light and near-infrared light in the incident light are more effectively reduced, and only light in the visible light region can be transmitted downward and emitted under a high oblique incidence characteristic.

Japanese Patent Application Publication No. 2014-148567

However, as studied by the present inventors, phosphate-based glass such as phosphate glass or fluorophosphate glass is usually used as a constituent material of the absorption glass substrate that absorbs ultraviolet light or near-infrared light, while various constituent materials of the absorption resin film are used. Although organic materials made of polymers are used, it has been found that the adhesion between the two is not necessarily sufficient, and that the adhesion is particularly likely to be insufficient in the presence of moisture.

Under such circumstances, the present invention aims to provide an optical filter provided with a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass, and also to provide an imaging device having the related optical filter. It is done.

In order to achieve the above object, the present inventor has intensively studied and found that an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass contains at least one type selected from Si atoms, Ti atoms, Zr atoms, and Al atoms. It was discovered that the above-described technical problem could be solved by an optical filter in which a resin film is provided using a bonding component, and the present invention was completed based on this finding.

That is, the present invention

(1) An absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; A bonding layer having a single-layer structure; and a resin film, wherein the resin film is provided on the absorption glass substrate through a bonding layer, and the bonding layer includes Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms. (hereinafter appropriately referred to as optical filter 1 of the present invention),

(2) In the bonding layer, the above ( The optical filter described in 1),

(3) For the absorption glass substrate made of phosphate-based glass or non-phosphate-based glass, the following general formula (I)

M(OSiR ¹ R ² R ³ ) _n (I)

(However, M is a Ti atom, a Zr atom, or an Al atom, and R ¹ , R ² and R ³ are linear or branched hydrocarbon groups of 1 to 10 carbon atoms that may contain an oxygen atom or a nitrogen atom, and are the same as each other. It may be different or different, and n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSiR ¹ R ² R ³ groups may be the same or different from each other.)

Compounds represented by and the following general formula (II)

(Ti _k O _{k - 1} )(OSiR ⁴ R ⁵ R ⁶ ) _{2k +2} (II)

(However, R ⁴ , R ⁵ and R ⁶ are linear or branched hydrocarbon groups with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and may be the same or different from each other, and k is 2 or more and 15 or less. is a real number, and a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.)

The optical filter according to (1) or (2) above, wherein a resin film is provided through a bonding layer containing a hydrolyzed, dehydrated condensate of at least one coupling agent selected from the compounds represented by (hereinafter, appropriately referred to as the optical filter of the present invention) (referred to as optical filter 1-1),

(4) For the absorption glass substrate made of phosphate-based glass or non-phosphate-based glass, the following general formula (III)

M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)

(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)

Compounds represented by and the following general formula (IV)

(Ti _k O _{k - 1} ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)

(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

The optical filter according to any one of (1) to (3) above, wherein a resin film is provided through a bonding layer containing a hydrolyzed, dehydrated condensate of at least one coupling agent selected from the compounds represented by (hereinafter, appropriately (referred to as optical filter 1-2 of the present invention),

(5) The coupling agent represented by the general formula (III) above has the following general formula (V)

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)

(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

A silicon compound represented by and the following general formula (VI)

Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)

(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)

Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)

(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)

Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)

(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

The optical filter according to (4) above, which consists of a reactant with at least one type selected from metal alkoxides represented by,

(6) The optical filter according to any one of (1) to (5) above, wherein the bonding layer further contains a dehydration condensate of silanol,

(7) For the absorption glass substrate made of phosphate-based glass or non-phosphate-based glass, the following general formula (V)

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)

(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

50 mol% or more but less than 100 mol% of a silicon compound represented by the following general formula (VI)

Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)

(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)

Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)

(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)

Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)

(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

The above (wherein a resin film is provided through a bonding layer containing a hydrolyzed and dehydrated condensate of a coupling agent composition containing a reactant with more than 0 mol% but not more than 50 mol% of at least one type selected from metal alkoxides represented by ( The optical filter according to any one of 1) to (6),

(8) The coupling agent composition contains more than 80 mol% but less than 100 mol% of a silicon compound represented by the general formula (V) and at least one metal alkoxide selected from the general formulas (VI) to (VIII) 0 The optical filter according to (7) above, which consists of a reactant with more than 20 mol% and less than 20 mol%,

(9) The coupling agent composition contains 85 to 94 mol% of a silicon compound represented by the general formula (V) and 6 to 15 moles of at least one metal alkoxide selected from the general formulas (VI) to (VIII). The optical filter according to (7) above, which consists of a reactant with %,

(10) An absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; and a resin film, wherein the resin film includes at least one selected from Ti atoms, Zr atoms, and Al atoms along with Si atoms, and the resin film is provided on an absorption glass substrate (hereinafter, appropriately referred to as an optical filter). called optical filter 2 of the invention),

(11) In the resin film, the above ( The optical filter described in 10),

(12) For an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass, the following general formula (I)

M(OSiR ¹ R ² R ³ ) _n (I)

(However, M is a Ti atom, a Zr atom, or an Al atom, and R ¹ , R ² and R ³ are linear or branched hydrocarbon groups of 1 to 10 carbon atoms that may contain an oxygen atom or a nitrogen atom, and are the same as each other. It may be different or different, and n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSiR ¹ R ² R ³ groups may be the same or different from each other.)

Compounds represented by and the following general formula (II)

(Ti _k O _{k - 1} )(OSiR ⁴ R ⁵ R ⁶ ) _{2k +2} (II)

(However, R ⁴ , R ⁵ and R ⁶ are linear or branched hydrocarbon groups with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and may be the same or different from each other, and k is 2 or more and 15 or less. is a real number, and a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.)

The optical filter according to (10) or (11) above, which is provided with a resin film containing a hydrolyzed, dehydrated condensate of at least one coupling agent selected from the compounds represented by (hereinafter, appropriately referred to as optical filter 2-1 of the present invention) It is called),

(13) For the absorption glass substrate made of phosphate-based glass or non-phosphate-based glass, the following general formula (III)

M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)

(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)

Compounds represented by and the following general formula (IV)

(Ti _k O _{k - 1} ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)

(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

The optical filter according to any one of (10) to (12) above, which is provided with a resin film containing a hydrolyzed, dehydrated condensate of at least one coupling agent selected from the compounds represented by (hereinafter, appropriately referred to as the optical filter of the present invention) (call it 2-2),

(14) The coupling agent represented by the general formula (III) above has the following general formula (V)

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)

(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

A silicon compound represented by and the following general formula (VI)

Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)

(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)

Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)

(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)

Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)

(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

The optical filter according to (13) above, which consists of a reactant with at least one type selected from metal alkoxides represented by,

(15) The optical filter according to any one of (10) to (14) above, wherein the resin film further contains a dehydration condensate of silanol,

(16) For an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass, the following general formula (V)

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)

(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

50 mol% or more but less than 100 mol% of a silicon compound represented by the following general formula (VI)

Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)

(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)

Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)

(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)

Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)

(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

(10) to (15) above, wherein a resin film is provided containing the hydrolysis and dehydration condensation product of a coupling agent composition containing a reactant with more than 0 mol% but not more than 50 mol% of one or more types of metal alkoxides represented by ) The optical filter described in any one of the following,

(17) The coupling agent composition contains more than 80 mol% but less than 100 mol% of the silicon compound represented by the general formula (V) and one or more metal alkoxides represented by the general formulas (VI) to (VIII) 0 The optical filter according to (16) above, which consists of a reactant with more than 20 mol% and less than 20 mol%,

(18) The coupling agent composition contains 85 to 94 mol% of a silicon compound represented by the general formula (V) and 6 to 15 mole of at least one metal alkoxide represented by the general formulas (VI) to (VIII). The optical filter according to (16) above, consisting of a reactant with %, and

(19) An imaging device comprising a solid-state imaging element, an imaging lens, and an optical filter according to any one of (1) to (18) above.

is to provide.

According to the present invention, it is possible to provide an optical filter provided with a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass, and also to provide an imaging device having the associated optical filter.

FIG. 1 is a schematic diagram of a camera module, FIG. 1(a) is a schematic diagram of a camera module for a compact digital camera, and FIG. 1(b) is a schematic diagram of a camera module for a digital SLR camera.
Figure 2 is a schematic diagram showing the structure of an infrared cut filter (IRCF) 1, and Figure 2(a) is a schematic diagram of a reflection type IRCF that reflects ultraviolet light and near-infrared light by a reflective film (UVIR film). 2(b) is a schematic diagram of a hybrid type IRCF having a reflective film (UVIR film), an absorbing glass substrate that absorbs ultraviolet light or near-infrared light, and an absorbing resin film that absorbs ultraviolet light or near-infrared light.
Fig. 3 is a cross-sectional image (image contrast) obtained by a scanning transmission electron microscope-energy dispersive X-ray spectrometer (STEM-EDX) of an example of an optical filter according to the present invention.
Fig. 4 is a diagram showing the STEM-EDX line (the EDX line (K line) detection intensity line in the depth direction of each element constituting the optical filter) in an example of the optical filter according to the present invention.

The optical filter 1 of the present invention includes an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; A bonding layer having a single-layer structure; and a resin film, wherein the resin film is provided on the absorbent glass substrate through a bonding layer, and the bonding layer includes Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms, Specific examples include optical filter 1-1 of the present invention or optical filter 1-2 of the present invention, which will be described later.

Additionally, the optical filter 2 of the present invention includes an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; and a resin film, wherein the resin film contains at least one selected from Ti atoms, Zr atoms, and Al atoms along with Si atoms, and the resin film is provided on an absorption glass substrate, the specific embodiment of which will be described later. Optical Filter 2-1 of the present invention or Optical Filter 2-2 of the present invention may be mentioned.

The optical filter 1 of the present invention and the optical filter 2 of the present invention are formed by interposing a bonding layer having a single-layer structure containing Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms on an absorption glass substrate. They differ in that they are formed by providing a resin film, or by providing a resin film containing Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms, and are common in other respects.

For this reason, the description of the optical filter of the present invention described below is assumed to be common to the optical filter 1 of the present invention and the optical filter 2 of the present invention unless otherwise specified.

[Glass substrate]

The optical filter according to the present invention has an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass as a glass substrate.

In the optical filter according to the present invention, the absorption glass substrate preferably has a thickness of 0.01 to 1.50 mm, more preferably 0.01 to 0.70 mm, and even more preferably 0.01 to 0.30 mm.

When the thickness of the absorption glass substrate is within the above range, thinning of the optical filter can be easily achieved.

In the optical filter according to the present invention, the absorbing glass substrate is made of phosphate-based glass or non-phosphate-based glass.

The phosphate-based glass in the present invention is a glass containing P and O as essential components and other optional components, and it is particularly preferable that it contains CuO. By containing CuO, the phosphate-based glass can absorb near-infrared light more effectively. Other optional components of phosphate-based glass include, for example, Ca, Mg, Sr, Ba, Li, Na, K, Cs, etc.

The fluorophosphate-based glass in the present invention is a glass containing P, O, and F as essential components and other optional components, and it is particularly preferable that it contains CuO. By containing CuO, the fluorophosphate-based glass can absorb near-infrared light more effectively. Other optional components of fluorophosphate-based glass include, for example, Ca, Mg, Sr, Ba, Li, Na, K, Cs, etc.

As the phosphate-based glass,

P ₂ O ₅ more than 0 mass% and less than 70 mass%,

Al ₂ O ₃ 0~40% by mass,

BaO 0-40% by mass,

CuO 0~40% by mass

It is desirable to include.

As the phosphate-based glass,

P ₂ O ₅ 20~60% by mass,

Al ₂ O ₃ 0-10% by mass,

BaO 0-10% by mass,

CuO 0~10% by mass

It is more preferable to include.

As the phosphate-based glass,

P ₂ O ₅ 20~60% by mass,

Al ₂ O ₃ 1 to 10% by mass,

BaO 1-10% by mass,

CuO 1-10% by mass

It is more preferable to include.

As the above fluorophosphate glass,

P ₂ O ₅ more than 0 mass% and less than 70 mass%,

Al ₂ O ₃ 0~40% by mass,

BaO 0-40% by mass,

CuO 0~40% by mass

Contains, and further contains more than 0% by mass and 40% by mass or less of fluoride.

It is desirable.

As the above fluorophosphate glass,

P ₂ O ₅ 20~60% by mass,

Al ₂ O ₃ 0-10% by mass,

BaO 0-10% by mass,

CuO 0~10% by mass

Contains, and further contains 1 to 30% by mass of fluoride.

It is more preferable.

As the above fluorophosphate glass,

P ₂ O ₅ 20~60% by mass,

Al ₂ O ₃ 1 to 10% by mass,

BaO 1-10% by mass,

CuO 1-10% by mass

Contains, and additionally contains 2 to 30% by mass of fluoride.

It is more desirable.

Examples of the fluoride include one or more types selected from MgF ₂ , CaF ₂ , SrF ₂ , etc.

The optical filter 1 of the present invention is characterized in that a resin film is provided on the glass substrate through a bonding layer having a single layer structure containing Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms. It is done.

In the optical filter 1 of the present invention, the bonding layer includes one containing a hydrolyzed and dehydrated condensate of a coupling agent described later.

In the optical filter 1 of the present invention, the bonding layer has a single layer structure containing Si atoms and one or more types selected from Ti atoms, Zr atoms, and Al atoms.

In this application document, the single-layer structure has the same composition from the measurement image (image contrast) or elemental analysis results obtained when measured by a scanning transmission electron microscope-energy dispersive X-ray spectrometer (STEM-EDX) under the following conditions. A branch refers to a layered structure that is specified to be made of a forming material.

<Measurement conditions>

Scanning transmission electron microscope: ARM200F manufactured by Nippon Electronics Co., Ltd.

Energy-dispersive X-ray spectroscopic analyzer: JED-2300T manufactured by Nippon Electronics Co., Ltd.

Sample preparation: Focused ion beam processing (FIB)

Acceleration Voltage: 200kV

Elemental analysis: EDX mapping (resolution: 256×256)

3 is a STEM-EDX image (image contrast) obtained under the above measurement conditions in an example of the optical filter according to the present invention. From the same figure, the optical filter is shown with respect to the absorption glass substrate G through the bonding layer B. It can be seen that the resin film R is provided and the bonding layer B has a single-layer structure.

In the optical filter 1 of the present invention, the thickness of the bonding layer is preferably 1000 nm or less, more preferably 10 to 500 nm, and even more preferably 30 to 300 nm.

When the thickness of the bonding layer is 1000 nm or less, it is easy to suppress the occurrence of unevenness during the formation of the bonding layer (during firing), and the film surface of the bonding layer can be easily made uniform.

Additionally, when the thickness of the bonding layer is 10 nm or more, the bonding layer can easily exhibit sufficient bonding strength, and the mechanical strength of the optical filter can be easily improved.

In addition, in this application document, the thickness of the bonding layer is the arithmetic mean value when the thickness of the bonding layer is measured at 50 points in the measurement image (image contrast) of the optical filter cross section obtained when measured using the above-described STEM-EDX. it means.

In the optical filter 1 of the present invention, the bonding layer includes Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms. It is preferable that at least one type selected from Ti atoms, Zr atoms, and Al atoms contained in the bonding layer together with Si atoms is a Ti atom.

Figure 4 illustrates the STEM-EDX line (EDX line (K line) detection intensity line in the depth direction of each element constituting the optical filter) of optical filter 1 according to the present invention measured under the conditions described above. will be. In the example shown in Fig. 4, a resin film containing C atoms and O atoms as main components (described later) is provided in the region at a distance of 0 to 980 nm from the surface, and Si atoms and Ti are in the region at a distance of 980 to 1150 nm from the surface. It can be seen that a bonding layer containing atoms and O atoms as main components is provided, and an absorption glass substrate containing P atoms, F atoms and O atoms as main components is provided in a region where the distance from the surface is greater than 1150 nm, The constituent elements of each region can be confirmed using the STEM-EDX line, and the thickness of the bonding layer, etc. can be confirmed.

In the example shown in FIG. 4, it can be seen that the bonding layer of optical filter 1 contains Ti atoms as well as Si atoms.

In the bonding layer constituting the optical filter 1 of the present invention, the ratio of the total number of atoms of Ti atoms, Zr atoms, and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms, and Al atoms (total number of atoms): α (Atomic %) is preferably greater than 0 atomic % and less than or equal to 33.3 atomic %, more preferably 9 to 33.3 atomic %, and even more preferably 12 to 33.3 atomic %.

In this application document, the ratio α (atoms %) means the value calculated by the method below.

(1) A STEM-EDX measurement of the optical filter was performed under the measurement conditions described above, and a STEM-EDX line (EDX line (K line) in the depth direction of each element constituting the optical filter) as illustrated in FIG. ) to obtain the detected intensity line).

(2) Integrated EDX-ray _{intensity of} Si atoms in the region _constituting the bonding layer Find _Al respectively.

(3) A k factor (a different correction factor for each atomic number depending on the acceleration voltage or detection efficiency) is added to the integrated intensity of each EDX line obtained in (2). For convenience, the k factor of the Si atom is hereinafter referred to as K _Si and the k factor of the Ti atom is The k factor of K _Ti and Zr atoms is K _Zr , and the k factor of Al atoms is K _Al .) can be considered to correspond to the weight ratio of each constituent element. For this reason, for example, the weight ratio A _Ti (% by weight) of Ti atoms constituting the bonding layer can be calculated by the following formula.

(4) Additionally, it can be considered that the value obtained by multiplying the EDX-ray integrated intensity For this reason, if the atomic weight of the Si atom is M _Si , the atomic weight of the Ti atom is M _Ti , the atomic weight of the Zr atom is M _Zr , and the atomic weight of the Al atom is M _Al , for example, the number of Ti atoms constituting the bonding layer is M Al. The ratio α _Ti (atomic %) can be calculated by the following formula.

Additionally, the ratio α (atomic %) of the total number of atoms of Ti atoms, Zr atoms, and Al atoms constituting the bonding layer can be calculated using the following formula.

For example, in the example shown in FIG. 4, Si atoms and Ti atoms are included in the bonding layer, but Zr atoms and Al atoms are not included, so the total number of atoms of Ti atoms, Zr atoms, and Al atoms constituting the bonding layer is The ratio α (atomic %) can be calculated by the following formula.

Additionally, in this application document, K _Si = 1.000, K _Ti = 1.033, K _Zr = 5.696, and K _Al = 1.050.

Embodiments of the optical filter 1 of the present invention include the optical filter 1-1 of the present invention and the optical filter 1-2 of the present invention.

The optical filter 1-1 of the present invention has the following general formula (I) for the absorption glass substrate:

M(OSiR ¹ R ² R ³ ) _n (I)

(However, M is a Ti atom, a Zr atom, or an Al atom, and R ¹ , R ² and R ³ are linear or branched hydrocarbon groups of 1 to 10 carbon atoms that may contain an oxygen atom or a nitrogen atom, and are the same as each other. It may be different or different, and n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSiR ¹ R ² R ³ groups may be the same or different from each other.)

Compounds represented by and the following general formula (II)

(Ti _k O _{k - 1} )(OSiR ⁴ R ⁵ R ⁶ ) _{2k +2} (II)

(However, R ⁴ , R ⁵ and R ⁶ are linear or branched hydrocarbon groups with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and may be the same or different from each other, and k is 2 or more and 15 or less. is a real number, and a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.)

A resin film is provided through a bonding layer containing a hydrolyzed and dehydrated condensate of at least one coupling agent selected from the compounds represented by .

In addition, the optical filter 1-2 of the present invention has the following general formula (III) on an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass.

M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)

(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)

Compounds represented by and the following general formula (IV)

(Ti _k O _{k - 1} ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)

(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

A resin film is provided through a bonding layer containing a hydrolyzed and dehydrated condensate of at least one coupling agent selected from the compounds represented by .

The compound represented by the general formula (III), which is a constituent of the bonding layer, is a more limited version of the compound represented by the general formula (I), and is also represented by the general formula (IV), which is a constituent of the bonding layer. The compounds are more limited to those represented by the general formula (II).

For this reason, hereinafter, as a description of the bonding layer of optical filter 1 of the present invention, a compound represented by the general formula (I) and a compound represented by the general formula (III), which are constituents of the bonding layer, and the compound represented by the general formula (II) and the compound represented by general formula (IV) will be sequentially explained, while the method of forming the bonding layer will be explained.

In the optical filter 1 of the present invention, the following general formula (I)

M(OSiR ¹ R ² R ³ ) _n (I)

M constituting the compound represented by is a Ti atom, a Zr atom, or an Al atom, and is preferably a Ti atom.

In the compound represented by the general formula (I), R ¹ , R ² and R ³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms which may include an oxygen atom or a nitrogen atom, and It is preferable that it is a straight-chain or branched hydrocarbon group of 1 to 4 carbon atoms which may contain an atom, and more preferably it is a straight-chain or branched hydrocarbon group of 1 to 3 carbon atoms which may contain an oxygen atom or a nitrogen atom.

R ¹ , R ² and R ³ are specifically linear, branched or cyclic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Etc., -C ₃ H ₆ (COO)CHCH ₂ , -CH ₂ (COO)CHCH ₂ , -C ₂ H ₄ (COO)CHCH ₂ , -C ₄ H ₈ (COO)CHCH ₂ , -C ₅ H ₁₀ (COO)CHCH ₂ , -C ₆ H ₁₂ (COO)CHCH ₂ , -C ₇ H ₁₄ (COO)CHCH ₂ , -C ₈ H ₁₆ (COO)CHCH ₂ , -C ₉ H ₁₈ (COO)CHCH ₂ , -C ₁₀ H ₂₀ (COO) CHCH ₂ and the like may be selected from linear, branched or cyclic hydrocarbon groups.

In the optical filter 1 according to the present invention, when the carbon numbers of R ¹ , R ² and R ³ are within the above range, it becomes easy to maintain an appropriate reaction rate between the silicon compound and the metal alkoxide, and a more homogeneous coupling agent is obtained. It becomes easier to prepare.

In addition, in the compound represented by general formula (I), the functional groups represented by R ¹ , R ² and R ³ bonded to the silicon atom may affect the bonding properties between the resin film and the bonding layer. Therefore, the bonding property between the resin film and the bonding layer can be adjusted by selecting appropriate R ¹ , R ² and R ³ groups depending on the resin film provided on the bonding layer.

Said R ¹ , R ² and R ³ may be the same or different from each other.

Moreover, n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSiR ¹ R ² R ³ groups may be the same or different from each other.

In the optical filter 1 of the present invention, the compound represented by general formula (I) is the following general formula (III)

M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)

(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)

Compounds represented by are included.

In the compound represented by the general formula (III), M is a Ti atom, a Zr atom, or an Al atom, and is preferably a Ti atom.

In the compound represented by the general formula (III), R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and are linear or branched hydrocarbon groups having 1 to 4 carbon atoms. It is preferable, and it is more preferable that it is a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

R ⁷ , R ⁸ and R ⁹ specifically represent linear or branched or cyclic hydrocarbon groups of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. and those selected from the like.

R ⁷ , R ⁸ and R ⁹ may be the same or different from each other.

In the optical filter 1 according to the present invention, when the carbon numbers of R ⁷ , R ⁸ and R ⁹ are within the above range, it becomes easy to maintain an appropriate reaction rate between the silicon compound and the metal alkoxide, and a more homogeneous coupling agent is obtained. It becomes easier to prepare.

Said R ⁷ , R ⁸ and R ⁹ may be the same or different from each other.

Additionally, n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.

The coupling agent represented by the general formula (III) has the following general formula (V)

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)

(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

A silicon compound represented by and the following general formula (VI)

Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)

(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)

Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)

(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)

Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)

(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

At least one type selected from metal alkoxides represented by

It is preferable that it consists of a reactant of and.

In the silicon compound represented by the general formula (V), the carbon number and specific examples of R ⁷ , R ⁸ and R ⁹ are as described above, and R ⁷ , R ⁸ and R ⁹ may be the same or different from each other. You can do it.

The silicon compound represented by the general formula (V) can be easily produced by partially hydrolyzing the corresponding silane alkoxide as follows.

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )(OR ^a )+H ₂ O→Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH+R ^a OH

(However, R ⁷ , R ⁸ , R ⁹ and R ^a are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

The preferred embodiments of the hydrocarbon groups R ⁷ , R ⁸ and R ⁹ are as described above, and the preferred embodiments of R ^a are the same as those of the hydrocarbon groups R ⁷ , R ⁸ and R ⁹ .

When all of the silane alkoxides are hydrolyzed, the reaction proceeds as follows to produce silanol Si(OH) ₄ .

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )(OR ^a )+4H ₂ O→Si(OH) ₄ +R ⁷ OH+R ⁸ OH+R ⁹ OH+R ^a OH

On the other hand, by partially hydrolyzing the silane alkoxide by controlling the amount of water used to hydrolyze it, a silicon compound represented by general formula (V) can be obtained as described above.

Titanium alkoxide represented by the general formula (VI) Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ), the general formula (VII) Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )( In the zirconium alkoxide represented by OR ²⁰ ) and the aluminum alkoxide represented by the general formula (VIII) Al(OR ²¹ )(OR ²² )(OR ²³ ), R ¹³ to R ²³ (R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ ) are straight-chain or branched hydrocarbon groups having 1 to 10 carbon atoms, and straight-chain hydrocarbon groups having 2 to 9 carbon atoms. Alternatively, it is preferable that it is a branched hydrocarbon group, and it is more preferable that it is a linear or branched hydrocarbon group having 3 to 8 carbon atoms.

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² or R ²³ specifically methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Examples include those selected from linear or branched hydrocarbon groups such as yl group, heptyl group, octyl group, nonyl group, and decyl group, and cyclic hydrocarbon groups.

R ¹³ , R ^{14 ,} R ¹⁵ , R 16 , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ may be the same or different from each other.

In the optical filter 1 according to the present invention, the carbon number of R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² or R ²³ is 2 or more, The stability of the metal alkoxide to moisture can be effectively improved, and by being 9 or less, an increase in the viscosity of the metal alkoxide can be suppressed and handling properties can be effectively improved.

A silicon compound represented by the general formula Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH and a titanium alkoxide Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR Taking ¹⁶ ) as an example, both reactions are thought to proceed as follows.

4Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH+Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ )

→Ti{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} ₄ +R ¹³ OH+R ¹⁴ OH+R ¹⁵ OH+R ¹⁶ OH

For 1 mole of titanium alkoxide represented by ^the general formula Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) in ^the reaction ^system , By reacting in the excessive presence of a silicon compound in which 4 mol or more of the silicon compound exists, it is thought that all titanium alkoxides present in the system react according to the above formula.

The optical filter 1 according to the present invention has the following general formula (III) for an absorbing glass substrate:

M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)

(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)

An example is one in which the resin film described later is provided through a bonding layer containing a hydrolyzed and dehydrated condensate of a coupling agent containing a compound represented by .

Taking the case where the coupling agent consisting of the compound represented by the general formula (III) is Ti{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} ₄ as an example, the coupling agent is as shown in the reaction formula below. Likewise, the hydrolysis reaction proceeds by adding water to the system.

Ti{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} ₄ +12H ₂ O→Ti{OSi(OH) ₃ } ₄ +4R ⁷ OH+4R ⁸ OH+4R ⁹ OH

The hydrolysis reaction can be performed, for example, under temperature conditions of 10 to 40°C, using a catalyst such as HCl as appropriate, and in the presence of an appropriate amount of water.

Next, a coating liquid containing a hydrolyzate of a coupling agent consisting of a compound represented by the above general formula (III) is applied to the absorbent glass substrate to form a coating film.

It is preferable that the concentration of the coupling agent composed of a compound represented by general formula (III) in the coating liquid is 0.1 to 10.0 mass%. In addition, the amount of the coating liquid applied to the absorption glass substrate is preferably 0.01 to 0.10 ml/cm ² .

Methods for applying the coating solution containing the hydrolyzate of the coupling agent include one or more coating methods selected from dip coating, cast coating, spray coating, and spin coating.

Then, the coating liquid for forming a resin film described later is applied on the coating film to form an absorbent resin coating film, and then appropriately heated to form [-Ti(OSiO ₃ ) ₃ -] as a dehydration condensate of the hydrolyzate of the coupling agent. A reactant expressed as _n (however, n is a positive integer) can be obtained.

It is believed that the dehydration condensate, together with the coupling agents, bonds strongly to the coupling agent and the absorption glass or the resin film, and for this reason, according to the present invention, it exhibits high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass. It is possible to easily provide optical filter 1 provided with a resin film.

In the optical filter 1 of the present invention, the bonding layer may further contain a hydrolyzed and dehydrated condensate of silanol.

That is, silanol Si(OH) ₄ generates dehydration condensate (Si-O-Si) ₂ as shown in the following reaction equation by appropriately heating.

Si(OH) ₄ →(Si-O-Si) ₂ +2H ₂ O

According to the present inventors' examination, the dehydration condensate of the silanol alone tends to lack adhesion to the absorption glass substrate or the resin film, especially in the coexistence of moisture, but the product represented by the general formula (I) or (III) It is believed that by using the hydrolyzate of the coupling agent made of the compound together with the dehydration condensation product obtained by dehydration condensation, the above-mentioned adhesion is improved by complementing each other.

The silanol is added to a coating liquid containing a hydrolyzate of a coupling agent consisting of a compound represented by the general formula (I) or (III), and then the related coating liquid is applied to an absorbent glass substrate to form a coating film. is formed, and then appropriately subjected to the heat treatment, thereby forming a dehydration condensation product of silanol together with [-Ti(OSiO ₃ ) ₃ -] _n (where n is a positive integer) of the hydrolyzate of the coupling agent. can be created.

The optical filter 1 of the present invention has the following general formula (V) on an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass:

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)

(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

50 mol% or more but less than 100 mol% of a silicon compound represented by the following general formula (VI)

Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)

(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)

Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)

(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)

Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)

(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

A resin film is provided through a bonding layer containing a hydrolyzed and dehydrated condensate of a coupling agent composition containing a reactant with more than 0 mol% and up to 50 mol% of one or more types of metal alkoxides represented by It is desirable.

When the amount of the metal alkoxide is 50 mol% or less, the applicability of the resulting coupling agent can be effectively improved.

In the optical filter 1 according to the present invention, the coupling agent composition contains 50 mol% to less than 100 mol% of the silicon compound represented by the general formula (V) and the general formula (VI), general formula (VII), and general formula ( It is preferable that it is a reaction composition with more than 0 mol% but not more than 50 mol% of at least one type selected from the metal alkoxides represented by VIII), and more than 80 mol% and less than 100 mol% of the silicon compound represented by the general formula (V). It is more preferable that it is a reaction composition of more than 0 mol% but less than 20 mol% of at least one metal alkoxide selected from the above general formula (VI), general formula (VII) and general formula (VIII). 85 to 94 mol% of a silicon compound represented by general formula (V) and 6 to 15 mol% of one or more metal alkoxides represented by general formula (VI), general formula (VII) and general formula (VIII) It is more preferable that it is a reaction composition with .

The reaction rate between the silicon compound represented by the general formula (V) and one or more metal alkoxides selected from the general formula (VI), general formula (VII), and general formula (VIII) is within the above range. As a result, it is possible to easily form a film that is not only homogeneous but also smooth and unlikely to peel off.

Details of the absorption glass substrate, the silicon compound represented by formula (V), the metal alkoxide represented by formula (VI), formula (VII), and formula (VIII) are as described above. .

In the optical filter 1 according to the present invention, the coupling agent composition includes a silicon compound represented by general formula (V) and a metal alkoxide represented by general formula (VI), general formula (VII), and general formula (VIII). By being a reactant reacted in proportion, a uniform application solution containing the above-mentioned coupling agent composition can be easily prepared, and a uniform film can be easily formed.

As described above, the silicon compound represented by the general formula (V) Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH and the titanium alkoxide Ti(OR ¹³ ) represented by the general formula (VI) ( Taking OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) as an example, both reactions proceed as follows.

4Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH+Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ )

→Ti{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} ₄ +R ¹³ OH+R ¹⁴ OH+R ¹⁵ OH+R ¹⁶ OH

When reacted in the presence of an excess of a silicon compound in which 4 mol or more of the silicon compound exists relative to 1 mol of the titanium alkoxide, it is believed that all of the titanium alkoxides present in the system react according to the above formula, so that the titanium alkoxide When the amount of the silicon compound per mole is less than 4 moles, alkoxy groups (OR ¹³ groups, OR ¹⁴ groups, OR ¹⁵ groups, OR ¹⁶ groups) remain in the titanium compound produced, and titanium with such alkoxy groups remains. If a large number of compounds are present, the titanium compound will precipitate in the coating solution, making it difficult to form a uniform film. For this reason, it is preferable to use a coupling composition reacted in the presence of a silicon compound in excess of the theoretical amount.

As described above, Ti{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} ₄ produced in the above reaction is appropriately hydrolyzed in the presence of a catalyst consisting of an inorganic acid such as HCl, thereby carrying out a hydrolysis reaction according to the following reaction formula. generates

Ti{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} ₄ +12H ₂ O→Ti{OSi(OH) ₃ } ₄ +4R ⁷ OH+4R ⁸ OH+4R ⁹ OH

Also, at this time, if an excessive amount of the silicon compound represented by general formula (V) is present in the system, hydrolysis occurs according to the following reaction equation and silanol Si(OH) ₄ is generated.

Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH+3H ₂ O→Si(OH) ₄ +R ⁷ OH+R ⁸ OH+R ⁹ OH

As described above, the hydrolyzate Ti{OSi(OH) ₃ } ₄ is obtained as a dehydration condensation product of the hydrolyzate by appropriately heat-treating [-Ti(OSiO ₃ ) ₃ -] _n (where n is defined) It is an integer.) You can obtain a reactant expressed as

In addition, as described above, the silanol Si(OH) ₄ generated by the above hydrolysis is also subjected to appropriate heat treatment to generate a dehydration condensation reaction shown in the following reaction equation to generate a dehydration condensation product (Si-O-Si) ₂ I order it.

Si(OH) ₄ →(Si-O-Si) ₂ +2H ₂ O

The dehydration condensation product of the silanol alone tends to lack adhesion to the absorption glass substrate or the resin film, especially in the coexistence of moisture, but by using it in combination with the dehydration condensation product of the hydrolyzate Ti{OSi(OH) ₃ } ₄ of the coupling agent. , it is thought that adhesion to the absorption glass substrate, etc. is improved by complementing each other.

In addition to the reaction product between the silicon compound represented by the general formula (V) and the metal alkoxide represented by the general formula (VI), general formula (VII), or general formula (VIII), the coupling agent composition further reacts. It may contain optional components such as a catalyst, pH adjuster, leveling agent, and anti-foaming agent.

In the optical filter 1 of the present invention, the following general formula (II)

(Ti _k O _{k - 1} )(OSiR ⁴ R ⁵ R ⁶ ) _{2k +2} (II)

(However, R ⁴ , R ⁵ and R ⁶ are linear or branched hydrocarbon groups with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and may be the same or different from each other, and k is 2 or more and 15 or less. is a real number, and a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.)

The compound represented by is different from that represented by the general formula (I) described above, and has a multimer structure (-Ti-O-Ti-) containing two or more Ti atoms in the molecule.

In the compound represented by general formula (II), R ⁴ , R ⁵ and R ⁶ are straight-chain or branched hydrocarbon groups having 1 to 10 carbon atoms which may include an oxygen atom or a nitrogen atom. It is preferable that it is a linear or branched hydrocarbon group having 1 to 4 carbon atoms, which may contain an oxygen atom or a nitrogen atom, and more preferably a linear or branched hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom or a nitrogen atom.

R ⁴ , R ⁵ and R ⁶ are specifically linear, branched or cyclic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. Etc., -C ₃ H ₆ (COO)CHCH ₂ , -CH ₂ (COO)CHCH ₂ , -C ₂ H ₄ (COO)CHCH ₂ , -C ₄ H ₈ (COO)CHCH ₂ , -C ₅ H ₁₀ (COO)CHCH ₂ , -C ₆ H ₁₂ (COO)CHCH ₂ , -C ₇ H ₁₄ (COO)CHCH ₂ , -C ₈ H ₁₆ (COO)CHCH ₂ , -C ₉ H ₁₈ (COO)CHCH ₂ , -C ₁₀ H ₂₀ (COO) CHCH ₂ and the like may be selected from linear, branched or cyclic hydrocarbon groups.

In the compound represented by general formula (II), when the carbon numbers of R ⁴ , R ⁵ and R ⁶ are within the above range, it becomes easier to maintain an appropriate reaction rate between the silicon compound and the metal alkoxide, and a more homogeneous reaction is achieved. It becomes easier to prepare the coupling agent.

In addition, in the compound represented by general formula (II), the functional groups represented by R ⁴ , R ⁵ and R ⁶ bonded to the silicon atom may affect the bonding properties between the resin film and the bonding layer. Therefore, the bonding property between the resin film and the bonding layer can be adjusted by selecting appropriate R ⁴ , R ⁵ and R ⁶ groups depending on the resin film provided on the bonding layer.

In the compound represented by general formula (II), k is a real number of 2 to 15, more preferably a real number of 4 to 10, and especially preferably 4, 7, or 10.

In the compound represented by general formula (II), when k is within the above range, a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass can be easily prepared.

In the compound represented by general formula (II), R ⁴ , R ⁵ and R ⁶ may be the same or different from each other.

Moreover, a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.

In optical filter 1 of the present invention, the compound represented by general formula (II) is the following general formula (IV)

(Ti _k O _{k - 1} ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)

(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

Compounds represented by are included.

R ¹⁰ , R ¹¹ and R ¹² , which constitute the compound represented by general formula (IV), are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and are linear or branched hydrocarbon groups having 1 to 4 carbon atoms. It is preferable, and it is more preferable that it is a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

R ¹⁰ , R ¹¹ and R ¹² specifically represent straight or branched or cyclic hydrocarbon groups of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. and those selected from the like.

R ¹⁰ , R ¹¹ and R ¹² may be the same or different from each other.

In the compound represented by general formula (IV), when the carbon numbers of R ¹⁰ , R ¹¹ and R ¹² are within the above range, it becomes easier to maintain an appropriate reaction rate between the silicon compound and the metal alkoxide, and a more homogeneous reaction is achieved. It becomes easier to prepare the coupling agent.

In the compound represented by general formula (IV), k is a real number of 2 to 15, more preferably a real number of 4 to 10, and especially preferably 4, 7, or 10.

Additionally, the plurality of -OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.

In the compound represented by general formula (IV), when k is within the above range, a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass can be easily prepared.

In the compound represented by general formula (IV), when k is 2, it can be represented by the following structural formula.

(However, the plurality of R ¹⁰ , R ¹¹ and R ¹² may be the same or different, and the plurality of -OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

In the compound represented by general formula (IV), when k is 3, it can be represented by the following structural formula.

(However, the plurality of R ¹⁰ , R ¹¹ and R ¹² may be the same or different, and the plurality of -OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

The coupling agent represented by the general formula (IV) is the general formula (IX) below:

Si(OR ¹⁰ )(OR ¹¹ )(OR ¹² )OH (IX)

(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)

A silicon compound represented by and the following formula

Ti(OH) ₄

It is preferable that it consists of a reactant with tetrahydroxy titanium represented by .

In the silicon compound represented by the general formula (IX), the carbon number and specific examples of R ¹⁰ , R ¹¹ and R ¹² are as described above, and R ¹⁰ , R ¹¹ and R ¹² may be the same or different from each other. You can do it.

The reaction between the silicon compound represented by the general formula (IX) Si(OR ¹⁰ )(OR ¹¹ )(OR ¹² )OH and tetrahydroxytitanium represented by the formula Ti(OH) ₄ is, for example, as follows. I think it's progressing.

6Si(OR ¹⁰ )(OR ¹¹ )(OR ¹² )OH+2Ti(OH) ₄

→Ti ₂ O{OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} ₆ +4H ₂ O

The compound represented by the general formula Ti ₂ O{OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} ₆ obtained by the above reaction corresponds to the case where k is 2 in the compound represented by the above general formula (IV) do.

In the presence of an excess of a silicon compound in which more than 6 moles of a silicon compound represented by the general formula Si(OR ¹⁰ )(OR ¹¹ )(OR ¹² )OH exist in the reaction system relative to ₂ moles of tetrahydroxytitanium (Ti(OH) 4 ) By reacting, it is believed that all tetrahydroxytitanium existing in the system reacts according to the above formula.

As optical filter 1 according to the present invention, the absorption glass substrate has the following general formula (IV)

(Ti _k O _{k - 1} ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)

(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

It is preferable that the resin film described later is provided through a bonding layer containing a hydrolyzed and dehydrated condensate of at least one coupling agent selected from the compounds represented by .

When the coupling agent consisting of the compound represented by the general formula (IV) is Ti ₂ O{OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} ₆ (in the compound represented by the general formula (IV) above, Taking the case where k is 2) as an example, the hydrolysis reaction of the coupling agent proceeds by adding water to the system as shown in the reaction equation below.

Ti ₂ O{OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} ₆ +18H ₂ O→

Ti ₂ O{OSi(OH) ₃ } ₆ +6R ¹⁰ OH+6R ¹¹ OH+6R ¹² OH

The hydrolysis reaction can be performed, for example, under temperature conditions of 10 to 40°C, using a catalyst such as HCl as appropriate, and in the presence of an appropriate amount of water.

Next, a coating liquid containing a hydrolyzate of a coupling agent consisting of a compound represented by the above general formula (IV) is applied to the absorbent glass substrate to form a coating film.

It is preferable that the concentration of the coupling agent composed of a compound represented by general formula (IV) in the coating liquid is 0.5 to 20 mass%. In addition, the amount of the coating liquid applied to the absorption glass substrate is preferably 0.005 to 0.5 ml/cm ² .

Methods for applying the coating solution containing the hydrolyzate of the coupling agent include one or more coating methods selected from dip coating, cast coating, spray coating, and spin coating.

Then, the coating liquid for forming a resin film, which will be described later, is applied on the coating film to form an absorbent resin coating film, and then appropriately heated to produce [-(TiO ₃ ) ₂ (SiO ₃ ) ₅ - as a dehydration condensate of the hydrolyzate. ] A reactant expressed as _m (however, m is a positive integer) can be obtained.

It is believed that the dehydration condensate, together with the coupling agents, bonds strongly to the coupling agent and the absorption glass or the resin film, and for this reason, according to the present invention, it has high adhesion to the absorption glass substrate made of phosphate-based glass or non-phosphate glass. Optical filter 1 provided with a resin film having can be easily provided.

In the optical filter 1 of the present invention, as described above, the bonding layer may further contain a hydrolyzed and dehydrated condensate of silanol.

That is, when silanol Si(OH) ₄ is appropriately heated, dehydration condensation product (Si-O-Si) ₂ is generated as shown in the reaction formula below.

Si(OH) ₄ →(Si-O-Si) ₂ +2H ₂ O

According to the present inventors' examination, the dehydration condensation product of the silanol alone tends to lack adhesion to the absorption glass substrate or the resin film, especially in the coexistence of moisture, but the product represented by the general formula (II) or (IV) It is believed that by using the hydrolyzate of the coupling agent made of the compound together with the dehydration condensation product obtained by dehydration condensation, the above-mentioned adhesion is improved by complementing each other.

The silanol is added to a coating liquid containing a hydrolyzate of a coupling agent consisting of a compound represented by the general formula (II) or (IV), and then the related coating liquid is applied to an absorbent glass substrate to form a coating film. By forming and then appropriately applying the heat treatment, a dehydration-condensation product of silanol can be produced along with a dehydration-condensation product of the hydrolyzate of the coupling agent.

Next, optical filter 2 of the present invention will be described.

The optical filter 2 of the present invention includes an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; and a resin film, wherein the resin film contains Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms, and the resin film is provided on the absorption glass substrate. Specific embodiments thereof include: Optical Filter 2-1 of the present invention or Optical Filter 2-2 of the present invention may be mentioned.

The optical filter 2-1 of the present invention has the following general formula (I) on an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass:

M(OSiR ¹ R ² R ³ ) _n (I)

(However, M is a Ti atom, a Zr atom, or an Al atom, and R ¹ , R ² and R ³ are linear or branched hydrocarbon groups of 1 to 10 carbon atoms that may contain an oxygen atom or a nitrogen atom, and are the same as each other. It may be different or different, and n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSiR ¹ R ² R ³ groups may be the same or different from each other.)

Compounds represented by and the following general formula (II)

(Ti _k O _{k - 1} )(OSiR ⁴ R ⁵ R ⁶ ) _{2k +2} (II)

(However, R ⁴ , R ⁵ and R ⁶ are linear or branched hydrocarbon groups with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and may be the same or different from each other, and k is 2 or more and 15 or less. is a real number, and a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.)

A resin film containing a hydrolyzed and dehydrated condensate of one or more coupling agents selected from the compounds represented by is provided.

In addition, the optical filter 2-2 of the present invention has the following general formula (III) for an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass.

M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)

(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)

Compounds represented by and the following general formula (IV)

(Ti _k O _{k - 1} ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)

(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)

This is achieved by providing a resin film containing the hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by.

In relation to the optical filter 1 of the present invention, the optical filter 2 of the present invention includes the components of the bonding layer (for example, a coupling agent or a hydrolyzed, dehydrated condensate of the coupling agent composition) in a resin film described later. Although it is different from the optical filter 1 above in some respects, it is common in other respects. For this reason, the details of the explanation of common matters are as described above.

In addition, in the resin film constituting the optical filter 2 of the present invention, the ratio of the total number of atoms of Ti atoms, Zr atoms, and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms, and Al atoms (total number of atoms) α (atomic %) is also preferably greater than 0 atomic % and less than or equal to 33.3 atomic %, more preferably 9 to 33.3 atomic %, and even more preferably 12 to 33.3 atomic %.

In addition, in this application document, the ratio α (atomic %) of the total number of atoms of Ti atoms, Zr atoms, and Al atoms constituting the resin film is also the total number of Ti atoms, Zr atoms, and Al atoms constituting the above-described bonding layer. It means a value calculated by performing a STEM-EDX measurement of an optical filter under the same measurement conditions as the atomic ratio α (atomic %).

As a method for manufacturing the optical filter 2 of the present invention, for example, a resin film forming liquid containing a hydrolyzate of the coupling agent composition (described later) is applied to an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass. A method of forming a coating film, followed by appropriate heat treatment, etc. to perform a dehydration condensation reaction is an example. By this manufacturing method, the coupling agent can be strongly bonded to each other or the hydrolysis and dehydration condensation product of the coupling agent and the absorbing glass substrate can be strongly bonded to form a desired optical filter.

[Resin film]

In the optical filter according to the present invention, the resin film includes, for example, an absorption resin film that absorbs ultraviolet light or near-infrared light, an anti-reflection film, a reflection amplification film, a protective film to prevent glass from blurring, and a film to improve the strength of glass. Reinforced membranes, water-repellent membranes, etc. may be mentioned.

Examples of the absorbing resin film that absorbs ultraviolet light or near-infrared light include those containing a near-infrared absorbing dye and a transparent resin, and it is preferable that the near-infrared absorbing dye is uniformly dissolved or dispersed in the transparent resin.

As the near-infrared absorbing dye constituting the absorption resin film, conventionally known dyes can be adopted, and include cyanine-based dyes, polymethine-based dyes, squarylium-based dyes, porphyrin-based dyes, metal dithiol complex-based dyes, phthalocyanine-based dyes, and dimonium-based dyes. At least one type selected from pigments and inorganic oxide particles is preferable, and at least one type selected from squarylium-based pigments, cyanine-based pigments, and phthalocyanine-based pigments is more preferable.

As the resin constituting the resin film, conventionally known transparent resins can be adopted, including acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, One or more types selected from polyparaphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamidoimide resin, polyolefin resin, cyclic olefin resin, and polyester resin can be mentioned.

The transparent resin preferably has a high glass transition point (Tg) from the viewpoint of transparency, solubility of the near-infrared absorbing dye in the transparent resin, and heat resistance, and specifically, polyester resin, polycarbonate resin, polyether sulfone resin, and polyarylate. At least one type selected from resin, polyimide resin, and epoxy resin is preferable, and at least one type selected from polyester resin and polyimide resin is more preferable.

As the polyester resin, at least one type selected from polyethylene terephthalate resin and polyethylene naphthalate resin is preferable.

In addition to the near-infrared absorbing dye and transparent resin, the resin film may further contain color correction dye, leveling agent, antistatic agent, heat stabilizer, light stabilizer, antioxidant, dispersant, flame retardant, lubricant, plasticizer, etc., to the extent that they do not impair the effect of the present invention. It may contain optional ingredients.

As described above, when the optical filter according to the present invention is optical filter 1 of the present invention, for example, a liquid containing the coupling agent composition is applied on an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass. A hydrolyzed hydrolyzed film is formed, and a resin film-forming liquid that absorbs at least one of ultraviolet light and near-infrared light is applied thereon to form a coating film.

In addition, when the optical filter according to the present invention is the optical filter 2 of the present invention, for example, a resin film forming liquid containing the coupling agent composition is applied to an absorption glass substrate made of phosphate-based glass or non-phosphate-based glass. Forms a coating film.

The resin film is prepared by dissolving or dispersing, for example, a pigment, a transparent resin, and, in the case of forming an infrared cut filter according to the second aspect of the present invention, a coupling agent and optional mixing ingredients in a solvent, , it can be formed by coating it, drying it, and further hardening it as needed.

The resin film forming liquid may contain a known surfactant such as a cationic, anionic, or nonionic surfactant.

For coating the resin film forming liquid, one or more coating methods selected from dip coating, cast coating, spray coating, spin coating, etc. can be employed.

A resin film can be formed by coating the above-mentioned resin film-forming liquid on a substrate and then drying it.

Examples of the optical filter according to the present invention include an infrared cut filter (IRCF).

When the optical filter according to the present invention is an infrared cut filter (IRCF), for example, as illustrated in FIG. 2(b), the lower surface of the absorption glass substrate 3' that absorbs ultraviolet light or near-infrared light (light emission) An infrared cut filter (IRCF) 1 has an absorbing resin film 5 on the surface side that additionally absorbs ultraviolet light or near-infrared light.

In the embodiment illustrated in FIG. 2(b), a reflective film (UVIR film) 2 is provided on the upper surface side (light incident surface side) of the absorption glass substrate 3' that absorbs ultraviolet light or near-infrared light, and the above-described An anti-reflection film (AR film) 4 is additionally provided on the lower surface of the absorption resin film 5 that absorbs external light or near-infrared light.

In the above example, the reflective film (UVIR film) may be any that transmits visible light and blocks light in the ultraviolet region and near-infrared region. Examples of such a reflective film (UVIR film) include those made of a dielectric multilayer film.

The dielectric multilayer film is composed of a dielectric multilayer film in which low refractive index dielectric films (low refractive index films) and high refractive index dielectric films (high refractive index films) are alternately laminated. The constituent materials of the high refractive index film are Ta ₂ O ₅ , TiO ₂ , One or more types selected from Nb ₂ O ₅ and the like can be mentioned, and TiO ₂ is preferable.

Furthermore, the constituent material of the low refractive index film may include one or more types selected from SiO ₂ , SiO _x N _y , etc., and SiO ₂ is preferable.

A dielectric multilayer film can also be used as an antireflection film (AR film).

According to the present invention, an infrared cut filter provided with a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass can be provided.

Next, the imaging device according to the present invention will be described.

The imaging device according to the present invention is characterized by having a solid-state imaging element, an imaging lens, and an optical filter according to the present invention.

Examples of solid-state imaging devices include image sensors such as CCD (Charge-Coupled Device) sensors and CMOS (Complementary Metal Oxide Semiconductor) sensors.

An example of the configuration of the imaging device according to the present invention includes the camera module illustrated in FIG. 1.

FIG. 1(a) is a schematic diagram of a camera module according to a compact digital camera mounted on a smartphone, etc., and the camera module shown in FIG. 1(a) includes a lens L (or lens) of 1 (or an integer n of 1 or more). (L1...Ln)), and has an optical filter 1 and an image sensor (IC) according to the present invention.

In addition, Figure 1(b) is a schematic diagram of a camera module according to a digital SLR camera, and the camera module shown in Figure 1(b) includes a lens (L), an optical filter 1 according to the present invention, a cover glass (CG), and an image. It has a sensor (IC).

According to the present invention, it is possible to provide an imaging device having an optical filter provided with a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass.

(Example)

Hereinafter, the present invention will be further explained by examples and comparative examples, but the present invention is not limited to the following examples.

(Examples 1 to 7, Comparative Example 1)

1. Preparation of coating solution containing coupling agent

(1) In a container, 0.3 mL of 0.5 N (mol/L) HCl aqueous solution and 2.2 mL of 2-methoxyethanol were weighed and mixed under sealing.

(2) Tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ) was added to the container, and mixed for 30 minutes under sealing to cause a reaction represented by the following reaction formula.

Si(OC ₂ H ₅ ) ₄ +H ₂ O→HO-Si(OC ₂ H ₅ ) ₃ +C ₂ H ₅ OH

Since all the water is consumed by the above reaction and hydroxyl radicals are generated, it was expected that even if an alkoxide of Ti, which has a high hydrolysis rate, is added, the hydroxide will not precipitate and the solution will become homogeneous.

(3) Titanium(IV)n-butoxide (Ti(OC ₄ H ₉ ) ₄ ) was further added to the container in the ratio shown in Table 1 and mixed for 30 minutes under seal to obtain a coating liquid containing a coupling agent. was prepared. In Table 1, HO-Si(OC ₂ H ₅ ) ₃ and Ti(OC ₄ H ₉ ) when the total of HO-Si(OC ₂ H ₅ ) ₃ and Ti(OC ₄ H ₉ ) ₄ is 100 mol%. The addition ratio of ₄ is described respectively.

Also, at this time, it is believed that a reaction represented by the following reaction equation occurred within the container.

4OH-Si(OC ₂ H ₅ ) ₃ +Ti(OC ₄ H ₉ ) ₄ →Ti(O-Si(OC ₂ H ₅ ) ₃ ) ₄ +4C ₄ H ₉ OH

2. Formation of coating film

With respect to the container containing the above-mentioned coupling agent-containing coating liquid, 1.2 mL of 0.5N HCl aqueous solution, 4.7 mL of water, and 8.1 mL of 2-methoxyethanol were further weighed and mixed under seal for 30 minutes to form a coating film forming liquid. It was prepared.

At this time, it is believed that a reaction represented by the following reaction equation occurred within the container.

Ti{(O-Si(OC ₂ H ₅ ) ₃ } ₄ +12H ₂ O→Ti{(O-Si(OH) ₃ } ₄ +12C ₂ H ₅ OH

HO-Si(OC ₂ H ₅ ) ₃ +3H ₂ O→Si(OH) ₄ +3C ₂ H ₅ OH

The obtained coating film forming liquid was applied at a concentration of 0.03 mL/cm ² on an absorption glass substrate made of fluorophosphate-based glass (CD700 manufactured by HOYA Co., Ltd., thickness 0.59 mm) using a spin coater.

The absorbent glass substrate coated with the coating film forming liquid is placed on a hot plate heated to 250°C and heated for 30 minutes to dehydrate and condense to form an absorbent glass substrate (hereinafter referred to as “evaluation substrate 1”) having a cured film (bonding layer) on the surface. It is called.) was produced.

In each of the above examples and comparative examples, a plurality of evaluation substrates 1 were produced, and (1) untreated, (2) boiled, and (3) treated with a highly accelerated life test device (PCT treated) as follows. prepared, or (4) treated with high temperature and high humidity.

The contents of the boiling treatment, highly accelerated life test device treatment (PCT treatment), and high temperature and high humidity treatment are as follows.

(Mercy processing)

The evaluation substrate is immersed in a boiling water bath and boiled continuously for 60 minutes, then the evaluation substrate is taken out and dried by nitrogen blowing.

(Highly accelerated life test device processing (PCT processing))

The evaluation board is placed in a highly accelerated life test device (EHS-411M manufactured by Spec Co., Ltd.), and pressurized at 0.13 MPa for 72 hours under conditions of a temperature of 135°C and a humidity of 85%, and then the evaluation board is taken out.

(High temperature and high humidity treatment)

The evaluation board is placed in a high-temperature, high-humidity tester (PL-2KPH manufactured by Spec Co., Ltd.), and processed for 1000 hours under conditions of a temperature of 85° C. and a humidity of 85%, and then the evaluation board is taken out.

Regarding the above (1) untreated evaluation board, (2) boiled evaluation board, (3) evaluation board treated with highly accelerated life test device (PCT treatment), and (4) evaluation board subjected to high temperature and high humidity treatment, JIS An adhesion cross cut test was performed on the surface on which the cured film was prepared in accordance with the provisions of 5600-5-6.

The test results at this time were classified based on the following evaluation criteria 0 to 5. The results are shown in Table 1.

0: The edge of the cut is completely smooth, and there is no peeling in any of the grid eyes.

1: There is small peeling of the laminate at the intersection of cuts. There is less than 5% peeling per unit area.

2: The paint film is peeling off along the edges of the cut and/or at the intersection. There is peeling of more than 5% and less than 15% per unit area.

3: The paint film has peeled off significantly, partially or completely, along the edge of the cut, and/or several parts of the eye have peeled off partially or completely. There is peeling of more than 15% and less than 35% per unit area.

4: The coating film has peeled off significantly, partially or completely, along the edge of the cut, and/or several spots have peeled off partially or completely. There is less than 35% peeling per unit area.

5: There is peeling of more than 35% per unit area.

(Example 8)

In Example 6, except that zirconium (IV) n-butoxide (Zr(OC ₄ H ₉ ) ₄ ) was used instead of titanium (IV) n-butoxide (Ti(OC ₄ H ₉ ) ₄ ). After preparing a coating liquid containing a coupling agent in the same manner as in 6, evaluation board 1 with a coating film was prepared, and a cross cut test was similarly performed. The results are shown in Table 2.

(Example 9)

In the same manner as Example 3, except that aluminum n-butoxide (Al(OC ₄ H ₉ ) ₃ ) was used instead of titanium (IV) n-butoxide (Ti(OC ₄ H ₉ ) ₄ ). After preparing the coating liquid containing the coupling agent, evaluation board 1 with a coating film was prepared, and a cross cut test was similarly performed. The results are shown in Table 3.

(Example 10 to Example 12)

1. Preparation of coating solution containing coupling agent

(1) In a container, 0.3 mL of 0.5 N (mol/L) HCl aqueous solution and 2.2 mL of 2-methoxyethanol were weighed and mixed under sealing.

(2) Tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ) was added to the container, and mixed for 30 minutes under seal to generate a reaction represented by the following reaction formula.

Si(OC ₂ H ₅ ) ₄ +H ₂ O→HO-Si(OC ₂ H ₅ ) ₃ +C ₂ H ₅ OH

Since all water is consumed by the above reaction and hydroxyl radicals are generated, it was expected that even if an alkoxide of Ti, which has a high hydrolysis rate, is added, hydroxide will not precipitate and the solution will become homogeneous.

(3) Tetra-n-butoxytitanium polymer (Ti ₄ O ₃ (OC ₄ H ₉ ) ₁₀ ) was further added to the container in the ratio shown in Table 4 and mixed for 30 minutes under seal to form a coupling agent. A containing coating liquid was prepared. Also, at this time, it is believed that a reaction represented by the following reaction equation occurred within the container.

10OH-Si(OC ₂ H ₅ ) ₃ +Ti ₄ O ₃ (OC ₄ H ₉ ) ₁₀ →Ti ₄ O ₃ (O-Si(OC ₂ H ₅ ) ₃ ) ₁₀ +10C ₄ H ₉ OH

Instead of Ti ₄ O ₃ (OC ₄ H ₉ ) ₁₀ (Example 10), Ti ₇ O ₆ (OC ₄ H ₉ ) ₁₆ (Example 11) and Ti ₁₀ O ₉ (OC ₄ H ₉ ) ₂₂ (Example 12) ) was used to prepare a coating liquid in the same way. Table 4 lists the mixing ratios of the silicon compound and titanium compound in each coating liquid. Additionally, the content ratio shown in Table 4 is based on the sum of HO-Si(OC ₂ H ₅ ) ₃ and each titanium compound represented by the general formula Ti _k O _{k -1} (OC ₄ H ₉ ) _{2k+ 2} as 100 mol%. It means the respective mixing ratios of HO-Si(OC ₂ H ₅ ) ₃ and titanium compounds.

2. Formation of coating film

Into the container containing the above-mentioned coupling agent-containing coating liquid, 1.2 mL of 0.5N HCl aqueous solution, 4.7 mL of water, and 8.1 mL of 2-methoxyethanol were additionally weighed and mixed under seal for 30 minutes to form a coating film forming liquid. was prepared.

For example, when Ti ₄ O ₃ (OC ₄ H ₉ ) ₁₀ was used, it is believed that a reaction represented by the following reaction formula occurred within the container.

Ti ₄ O ₃ {O-Si(OC ₂ H ₅ ) ₃ } ₁₀ +30H ₂ O→Ti ₄ O ₃ {(O-Si(OH) ₃ } ₁₀ +30C ₂ H ₅ OH

HO-Si(OC ₂ H ₅ ) ₃ +3H ₂ O→Si(OH) ₄ +3C ₂ H ₅ OH

The obtained coating film forming liquid was applied at a concentration of 0.03 mL/cm ² on an absorption glass substrate made of fluorophosphate-based glass (CD700 manufactured by HOYA Co., Ltd., thickness 0.59 mm) using a spin coater.

The absorbent glass substrate coated with the coating film forming liquid was placed on a hot plate heated to 250°C and dehydrated and condensed for 30 minutes to produce an absorbent glass substrate (evaluation substrate 1) having a cured film (bonding layer) on the surface.

3. Formation of resin film

A resin film was further formed on the absorbent glass substrate having a cured film (bonding layer) on the surface obtained through the above process according to the following procedure.

(1) 0.2 g of polyvinyl butyral resin and 1.8 g of cyclopentanone were weighed in a container and mixed under sealing.

(2) 0.09 g of toluene diisocyanate was added to the container and mixed under seal to prepare a resin film forming liquid.

(3) The obtained resin film forming liquid was applied at a concentration of 0.03 mL/cm ² to an absorbent glass substrate having a cured film (bonding layer) on the surface obtained by the above process using a spin coater.

(4) The absorbed glass substrate coated with the resin film forming solution was placed on a hot plate heated to 160°C and cured by heating for 20 minutes to produce a glass substrate (evaluation substrate 2) having a resin film on the surface.

In Examples 10 to 12, for evaluation substrate 1 on which only the cured film (bonding layer) was formed and evaluation substrate 2 on which a resin film was additionally formed on the bonding layer, (1) untreated and (1) untreated and ( 2) Boiling treatment was prepared in the same manner as Examples 1 to 9.

For the (1) untreated evaluation substrate and (2) the boiling-treated evaluation substrate, the surface on which the cured film (bonding layer) of the evaluation substrate 1 was provided in accordance with the provisions of JIS 5600-5-6 described above or the above An adhesion cross cut test was performed on the surface of the evaluation substrate 2 on which the resin film was provided, and evaluation was performed based on evaluation criteria 0 to 5 in the same manner as Examples 1 to 9. The results are shown in Table 4.

Additionally, in evaluation substrate 2 obtained in Example 11, a STEM-EDX measurement was performed to obtain a STEM-EDX line (EDX line detection intensity line in the depth direction of each element constituting the optical filter), and a bonding layer portion was formed. The content ratio α (atomic %) of Ti atoms to the total number of Si atoms and Ti atoms and the content ratio β (atomic %) of Si atoms to the total number of Si atoms and Ti atoms are determined by the following equations, respectively. calculated.

₍ In _{addition ,} (Correction coefficient), K _Ti refers to the k factor (correction coefficient) of Ti atoms, M _Si refers to the atomic weight of Si atoms, and M _Ti refers to the atomic weight of Ti atoms.)

The results are shown in Table 5.

Mixing ratio (mol%) Crosscut test results for evaluation board 1 OH-Si(OC ₂ H ₅ ) ₃ Ti(OC ₄ H ₉ ) ₄ (One)
unprocessed (2)
mercy treatment (3)
PCT processing (4)
High temperature and high humidity treatment Comparative Example 1 100 0 - 5 5 - Example 1 97 3 - One 5 - Example 2 94 6 - One 5 - Example 3 91 9 - 0 One - Example 4 88 12 0 0 0 - Example 5 85 15 0 0 0 - Example 6 82 18 - 0 0 0 Example 7 80 20 0 0 - -

Mixing ratio (mol%) Crosscut test results for evaluation board 1 OH-Si(OC ₂ H ₅ ) ₃ Zr(O C ₄ H ₉ ) ₄ (One)
unprocessed (2)
mercy treatment (3)
PCT processing (4)
High temperature and high humidity treatment Example 8 82 18 - 0 - -

Mixing ratio (mol%) Crosscut test results for evaluation board 1 OH-Si(OC ₂ H ₅ ) ₃ Al(OC ₄ H ₉ ) ₃ (One)
unprocessed (2)
mercy treatment (3)
PCT processing (4)
High temperature and high humidity treatment Example 9 91 9 - 0 - -

Mixing ratio (mol%) Cross Cut Test Results Evaluation board 1
(bonding layer) Evaluation Board 2
(resin film) OH-Si(OC ₂ H ₅ ) ₃ Ti _k O _{k -1} (OC ₄ H ₉ ) _2k+2 k (One)
unprocessed (2)
mercy treatment (One)
unprocessed (2)
mercy treatment Example 10 91 9 4 - 0 0 One Example 11 94 6 7 0 0 0 One Example 12 96 4 10 0 0 0 One

Mixing ratio (mol%) Content ratio (atomic %) OH-Si(OC ₂ H ₅ ) ₃ Ti _k O _{k -1} (OC ₄ H ₉ ) _2k+2 k Ti atom content ratio α Si atom content ratio β Example 11 94 6 7 22 78

From Tables 1 to 3, in Examples 1 to 9, the cured film formed on the absorption glass substrate was a specific coupling agent represented by the general formula M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n. Since it is a cured film (bonding layer) containing a hydrolyzed and dehydrated condensate of , it can be seen that it has high adhesion to the absorption glass substrate.

Additionally, from Tables 4 to 5, in Examples 10 to 12, the cured film (bonding layer) or resin film formed on the absorption glass substrate had the general formula (Ti _k O _{k - 1} ) {OSi (OR ¹⁰ ) (OR ¹¹ )(OR ¹² )} _{2k+ 2} In that it is a resin film formed on a cured film (bonding layer) or a related cured film (bonding layer) containing the hydrolysis and dehydration condensate of a specific coupling agent, It can be seen that it has high adhesion to the absorption glass substrate. In particular, in Examples 10 to 12, although the mixing ratio (mol%) of the titanium compound constituting the cured film is low, compared to Examples 1 to 3 where the mixing ratio (mol%) of the titanium compound is about the same. It can be seen that adhesion is excellent. For this reason, it can be seen that using a multimer rather than a monomer as a titanium compound can demonstrate excellent adhesion at a lower content ratio.

On the other hand, from Table 1, in Comparative Example 1, the cured film (bonding layer) formed on the absorption glass substrate does not contain hydrolysis or dehydration condensation products of a specific coupling agent, so that the absorption glass substrate It can be seen that the adhesion to is poor.

According to the present invention, an infrared cut filter provided with a resin film having high adhesion to an absorption glass substrate made of phosphate-based glass or non-phosphate glass can be provided, and an imaging device having the related infrared cut filter can be provided.

One… Optical filter (infrared cut filter (IRCF))
2… Reflective membrane (UVIR membrane)
3… glass substrate
3'… Absorbent glass substrate
4… Anti-reflective film (AR film)
5… absorption resin film
L… lens
CG… cover glass
IC… image sensor

Claims (19)

An absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; A bonding layer having a single-layer structure; and an optical filter comprising a resin film,
A resin film is provided on the absorbent glass substrate through a bonding layer,
The bonding layer includes a hydrolyzed and dehydrated condensate of one or more coupling agents, and the coupling agent is a silicon compound containing a Si atom and a metal alkoxide containing one or more selected from Ti atoms, Zr atoms, and Al atoms. A reactant, an optical filter. The method according to claim 1, wherein in the bonding layer, the ratio of the total number of Ti atoms, Zr atoms, and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms, and Al atoms is greater than 0 at% and 33.3 at%. An optical filter characterized by the following. The absorption glass substrate according to claim 1, which is made of phosphate-based glass or non-phosphate-based glass, has the following general formula (I):
M(OSiR ¹ R ² R ³ ) _n (I)
(However, M is a Ti atom, a Zr atom, or an Al atom, and R ¹ , R ² and R ³ are linear or branched hydrocarbon groups of 1 to 10 carbon atoms that may contain an oxygen atom or a nitrogen atom, and are the same as each other. It may be different or different, and n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSiR ¹ R ² R ³ groups may be the same or different from each other.)
Compounds represented by and the following general formula (II)
(Ti _k O _k-1 )(OSiR ⁴ R ⁵ R ⁶ ) _2k+2 (II)
(However, R ⁴ , R ⁵ and R ⁶ are linear or branched hydrocarbon groups with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and may be the same or different from each other, and k is 2 or more and 15 or less. is a real number, and a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.)
An optical filter comprising a resin film provided through a bonding layer containing a hydrolyzed and dehydrated condensate of at least one coupling agent selected from the compounds represented by . The absorption glass substrate according to claim 1, which is made of phosphate-based glass or non-phosphate-based glass, has the following general formula (III):
M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)
(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)
Compounds represented by and the following general formula (IV)
(Ti _k O _k-1 ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)
(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)
An optical filter comprising a resin film provided through a bonding layer containing a hydrolyzed and dehydrated condensate of at least one coupling agent selected from the compounds represented by . The method of claim 4, wherein the coupling agent represented by the general formula (III) has the following general formula (V)
Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)
(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
A silicon compound represented by and the following general formula (VI)
Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)
(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)
Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)
(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)
Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)
(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
An optical filter characterized in that it consists of a reactant with one or more types selected from metal alkoxides represented by . The optical filter according to claim 1, wherein the bonding layer further includes a dehydration condensate of silanol. The absorption glass substrate according to claim 1, which is made of phosphate-based glass or non-phosphate-based glass, has the following general formula (V):
Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)
(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
50 mol% or more but less than 100 mol% of a silicon compound represented by the following general formula (VI)
Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)
(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)
Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)
(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)
Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)
(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
A resin film is provided through a bonding layer containing a hydrolyzed and dehydrated condensate of a coupling agent composition containing a reactant with more than 0 mol% but not more than 50 mol% of one or more types of metal alkoxides represented by optical filter. The method of claim 7, wherein the coupling agent composition contains more than 80 mol% but less than 100 mol% of the silicon compound represented by the general formula (V) and at least one metal selected from the general formulas (VI) to (VIII). An optical filter characterized in that it consists of a reactant with more than 0 mol% and less than 20 mol% of alkoxide. The method of claim 7, wherein the coupling agent composition comprises 85 to 94 mol% of a silicon compound represented by the general formula (V) and at least one metal alkoxide 6 selected from the general formulas (VI) to (VIII). An optical filter characterized in that it consists of a reactant with ~15 mol%. An absorption glass substrate made of phosphate-based glass or non-phosphate-based glass; and an optical filter comprising a resin film,
The resin film contains a hydrolysis and dehydration condensation product of at least one coupling agent, and the coupling agent is a silicon compound containing a Si atom and a metal alkoxide containing at least one selected from Ti atoms, Zr atoms, and Al atoms. An optical filter, wherein the reactant is a resin film provided on an absorbing glass substrate. 11. The resin film according to claim 10, wherein in the resin film, the ratio of the total number of atoms of Ti atoms, Zr atoms, and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms, and Al atoms is greater than 0 at% and 33.3 at%. An optical filter characterized by the following. 11. The method of claim 10, wherein the absorption glass substrate made of phosphate-based glass or non-phosphate-based glass has the following general formula (I):
M(OSiR ¹ R ² R ³ ) _n (I)
(However, M is a Ti atom, a Zr atom, or an Al atom, and R ¹ , R ² and R ³ are linear or branched hydrocarbon groups of 1 to 10 carbon atoms that may contain an oxygen atom or a nitrogen atom, and are the same as each other. It may be different or different, and n is 4 when M is a Ti atom or Zr atom and 3 when M is an Al atom, and the plurality of -OSiR ¹ R ² R ³ groups may be the same or different from each other.)
Compounds represented by and the following general formula (II)
(Ti _k O _k-1 )(OSiR ⁴ R ⁵ R ⁶ ) _2k+2 (II)
(However, R ⁴ , R ⁵ and R ⁶ are linear or branched hydrocarbon groups with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and may be the same or different from each other, and k is 2 or more and 15 or less. is a real number, and a plurality of -OSiR ⁴ R ⁵ R ⁶ groups may be the same or different from each other.)
An optical filter comprising a resin film containing a hydrolyzed and dehydrated condensate of at least one coupling agent selected from the compounds represented by . The absorption glass substrate according to claim 10, which is made of phosphate-based glass or non-phosphate-based glass, has the following general formula (III):
M{OSi(OR ⁷ )(OR ⁸ )(OR ⁹ )} _n (III)
(However, M is a Ti atom, Zr atom, or Al atom, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, and n is M In the case of this Ti atom or Zr atom, it is 4, and in the case where M is an Al atom, it is 3, and the plurality of -OSi(OR ⁷ )(OR ⁸ )(OR ⁹ ) groups may be the same or different from each other.)
Compounds represented by and the following general formula (IV)
(Ti _k O _k-1 ){OSi(OR ¹⁰ )(OR ¹¹ )(OR ¹² )} _2k+2 (IV)
(However, R ¹⁰ , R ¹¹ and R ¹² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other, k is a real number from 2 to 15, and a plurality of -OSi ( OR ¹⁰ )(OR ¹¹ )(OR ¹² ) groups may be the same or different from each other.)
An optical filter comprising a resin film containing a hydrolyzed and dehydrated condensate of at least one coupling agent selected from the compounds represented by . The method of claim 13, wherein the coupling agent represented by the general formula (III) has the following general formula (V)
Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)
(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
A silicon compound represented by and the following general formula (VI)
Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)
(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)
Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)
(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)
Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)
(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
An optical filter characterized in that it consists of a reactant with one or more types selected from metal alkoxides represented by . The optical filter according to claim 10, wherein the resin film further contains a dehydration condensate of silanol. 11. The method of claim 10, wherein the absorption glass substrate made of phosphate-based glass or non-phosphate-based glass has the following general formula (V):
Si(OR ⁷ )(OR ⁸ )(OR ⁹ )OH (V)
(However, R ⁷ , R ⁸ and R ⁹ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
50 mol% or more but less than 100 mol% of a silicon compound represented by the following general formula (VI)
Ti(OR ¹³ )(OR ¹⁴ )(OR ¹⁵ )(OR ¹⁶ ) (VI)
(However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.), general formula (VII)
Zr(OR ¹⁷ )(OR ¹⁸ )(OR ¹⁹ )(OR ²⁰ ) (VII)
(However, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.) and the following general formula (VIII)
Al(OR ²¹ )(OR ²² )(OR ²³ ) (VIII)
(However, R ²¹ , R ²² and R ²³ are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and may be the same or different from each other.)
An optical filter characterized by providing a resin film containing a hydrolyzed and dehydrated condensate of a coupling agent composition containing a reaction product of more than 0 mol% and not more than 50 mol% of at least one type selected from metal alkoxides represented by . The method of claim 16, wherein the coupling agent composition contains more than 80 mol% but less than 100 mol% of a silicon compound represented by the general formula (V) and one or more metals represented by the general formulas (VI) to (VIII). An optical filter characterized in that it consists of a reactant with more than 0 mol% and less than 20 mol% of alkoxide. The method of claim 16, wherein the coupling agent composition contains 85 to 94 mol% of a silicon compound represented by the general formula (V) and at least one metal alkoxide 6 represented by the general formulas (VI) to (VIII). An optical filter characterized in that it consists of a reactant with ~15 mol%. An imaging device comprising a solid-state imaging element, an imaging lens, and the optical filter according to any one of claims 1 to 18.